US5117043A - Process for the preparation of n-sulfomethylglycinate - Google Patents
Process for the preparation of n-sulfomethylglycinate Download PDFInfo
- Publication number
- US5117043A US5117043A US07/388,570 US38857089A US5117043A US 5117043 A US5117043 A US 5117043A US 38857089 A US38857089 A US 38857089A US 5117043 A US5117043 A US 5117043A
- Authority
- US
- United States
- Prior art keywords
- process according
- formaldehyde
- formula
- moles
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 16
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000004471 Glycine Substances 0.000 claims abstract description 7
- IWTOEMVHPMYHPE-UHFFFAOYSA-N 2-(sulfomethylamino)acetic acid Chemical compound OC(=O)CNCS(O)(=O)=O IWTOEMVHPMYHPE-UHFFFAOYSA-N 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 3
- 239000003586 protic polar solvent Substances 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 11
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004009 herbicide Substances 0.000 abstract description 7
- 239000005562 Glyphosate Substances 0.000 abstract description 6
- 229940097068 glyphosate Drugs 0.000 abstract description 6
- 150000001733 carboxylic acid esters Chemical group 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract 1
- -1 alkylthio radicals Chemical class 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- HHOSMYBYIHNXNO-UHFFFAOYSA-N 2,2,5-trimethylhexane Chemical compound CC(C)CCC(C)(C)C HHOSMYBYIHNXNO-UHFFFAOYSA-N 0.000 description 2
- UNDXPKDBFOOQFC-UHFFFAOYSA-N 4-[2-nitro-4-(trifluoromethyl)phenyl]morpholine Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1N1CCOCC1 UNDXPKDBFOOQFC-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MXBSFLKBEREMCG-UHFFFAOYSA-N [(2-ethoxy-2-oxoethyl)amino]methanesulfonic acid Chemical compound CCOC(=O)CNCS(O)(=O)=O MXBSFLKBEREMCG-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 159000000032 aromatic acids Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 235000019502 Orange oil Nutrition 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Definitions
- the present invention relates to N-sulfomethyl glycinate compounds, a process for the preparation of these compounds and the use of these compounds for the preparation of herbicides of the glyphosate type.
- Glyphosate (N-phosphonomethylglycine) and its salts are wide-spectrum herbicides which are well known in the art. These herbicides and the processes for obtaining them are described, for example, in the following patents: U.S. Pat. No. 3,799,758; U.S. Pat. No. 3,835,000; U.S. Pat. No. 3,868,407; U.S. Pat. No. 3,950,402; U.S. Pat. No. 4,083,893; U.S. Pat. No. 4,147,719 and EP-A-0,019,384. Furthermore, the compound N-sulfomethylglycine is known from U.S. Pat. No. 4,069,048.
- the subject of the invention is to suggest a way of arriving at the glyphosate-type herbicides which has numerous advantages: economy, restricted number of stages, excellent yields and ease of development to the industrial scale.
- the invention relates to a N-sulfomethyl glycinate of formula:
- COOR 1 is a hydrolyzable carboxylic ester group.
- Hydrolyzable groups are well known in the art. Within the scope of the present invention, a hydrolyzable COOR 1 group is understood to mean all the groups which can be lyzed in the presence of water, optionally in an acid or basic medium, to give the corresponding --COOH acid and R 1 OH alcohol.
- a hydrolyzable COOR 1 group is understood to mean a group in which the R 1 radical is in particular chosen from the following radicals:
- radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy or alkylthio radicals, the aryl or aralkyl radicals being capable, in addition, of comprising 1 to 4 hetero atoms chosen from the atoms of oxygen, sulfur and nitrogen (for example furyl, thiophenyl or pyridyl).
- R 1 is chosen from the C 1 -C 6 alkyl or C 6 -C 10 aryl or C 7 -C 11 aralkyl groups, the said radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy radicals.
- One preparation process consists in putting formaldehyde, sulfur dioxide and a glycinate of formula: H 2 N--CH 2 --COOR 1 in contact.
- the reaction is preferably carried out with the following molar proportions:
- the reaction is generally carried out between 0° and 100° C., preferably between 10° C. and 90° C., by simply mixing the reactants.
- the formaldehyde is used in one or another easily accessible forms. According to the most usual form it is used in the form of an aqueous solution of concentration between 1% and saturation, preferably from 30 to 40%.
- the reaction may be carried out in the presence of an inert solvent; sometimes such a solvent is useless because the reaction medium normally contains water, particularly as a result of the use of formaldehyde in aqueous solution.
- saturated aliphatic hydrocarbons such as n-pentane, isopentane, 2-methylhexane and 2,2,5-trimethylhexane
- aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene
- saturated aliphatic ethers such as tetrahydrofuran and isopentylether
- aromatic ethers such as benzylethyl ether
- saturated aliphatic or aromatic ketones such as methyl ethyl ketone, methylisobutyl ketone and acetophenone
- saturated aliphatic or aromatic halogenated hydrocarbons such as fluorobenzene, 1-chloro-2-methylpropane and isobutyl chloride
- saturated aliphatic or aromatic esters such as isobutyl isobutyrate, ethyl acetate and methyl benzoate
- the saturated aliphatic or aromatic alcohols such as methanol, ethanol, isopropanol and phenol
- saturated aliphatic or aromatic acids such as acetic acid and benzoic acid
- Another particularly advantageous and unexpected preparation process consists in reacting formaldehyde, sulfur dioxide, an alcohol of the formula R OH and glycine of formula H 2 N--CH 2 --COOH.
- the reaction is preferably carried out with the following molar proportions:
- the R 1 OH alcohol will be used as solvent, the other aprotic solvents mentioned above being capable of being used, optionally, as cosolvents.
- ethanol will be chosen as solvent.
- the reaction is, otherwise, carried out in the same conditions as above.
- the subject of the invention is also the use of compounds of formula (I) in the preparation of known herbicides of the glyphosate type, the use consisting in putting the compound of formula (I) in contact with a phosphite of formula:
- a hydrolyzable (R 2 O) 2 P(O) group is understood to mean a group which, under the action of water, optionally in an acid or basic medium, is lyzed to an alcohol R 2 OH and an acid (O)P(OH) 2 .
- a hydrolyzable (R 2 O) 2 P(O) group is understood to mean a group the R 2 radical of which is in particular chosen from the following radicals:
- radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy or alkylthio radicals, the aryl or aralkyl radicals being capable, in addition, of comprising 1 to 4 hetero atoms chosen from the atoms of oxygen, sulfur and nitrogen (for example furyl, pyridyl and thiophenyl).
- R 2 is chosen from the C 1 -C 6 alkyl or C 6 -C 10 aryl or C 7 -C 11 aralkyl groups, the said radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy radicals.
- the reaction is carried out in the bulk phase or in an inert solvent.
- saturated aliphatic hydrocarbons such as n-pentane, isopentane, 2-methylhexane and 2,2,5-trimethylhexane
- aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene
- saturated aliphatic ethers such as tetrahydrofuran and isopentylether
- aromatic ethers such as benzylethyl ether
- saturated aliphatic or aromatic ketones such as methyl ethyl ketone, methylisobutyl ketone and acetophenone
- saturated aliphatic or aromatic halogenated hydrocarbons such as fluorobenzene, 1-chloro-2-methylpropane and isobutyl chloride
- saturated aliphatic or aromatic esters such as isobutyl isobutyrate, ethyl acetate and methyl benzoate
- the saturated aliphatic or aromatic alcohols such as methanol, isopropanol and phenol
- the saturated aliphatic or aromatic acids such as acetic acid and benzoic acid
- the reaction temperature is between 50° C. and 250° C. or the boiling point of the solvent, and preferably 100° to 200° C.
- the compound of formula (III) is a product which is known from the document EP 0,135,454. It may be hydrolyzed in a known manner to arrive at the N-phosphonomethylglycine or glyphosate herbicide.
- Glycine (7.5 g; 100 millimoles), 95% ethanol (120 cc) and a 31.5% aqueous solution of formaldehyde (19 g; 200 millimoles) are introduced successively into a two-necked flask provided with an alcohol thermometer.
- the suspension obtained is saturated with SO 2 until it has completely dissolved (increase of the temperature to 45° C.).
- ethyl sulfomethylglycinate (18.8 g) is obtained in a purity greater than 95% (determined by NMR at 360 MHz): this is a 95.5% yield with respect to the starting glycine.
- Ethyl sulfomethylglycinate (2.46 g; 12.5 millimoles), xylene (20 cc) and diisopropyl phosphite (2.07 g; 12.5 mmol) are introduced successively into a two-necked flask provided with a thermometer and a means of cooling.
- the suspension is heated for 1 h at 105° C., and after evaporation of the solvent under a vacuum provided by a water-jet pump an orange oil (3.81 g) is recovered, which is shown by titration to contain 40% protected glyphosate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Soil Working Implements (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/844,728 US5187292A (en) | 1988-08-18 | 1992-03-02 | N-sulfomethylglycinate, use in the preparation of herbicides of the glyphosate type |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8811141A FR2635522B1 (fr) | 1988-08-18 | 1988-08-18 | N-sulfonomethylglycinate procede de preparation, utilisation dans la preparation d'herbicides de type glyphosate |
| FR8811141 | 1988-08-18 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/844,728 Division US5187292A (en) | 1988-08-18 | 1992-03-02 | N-sulfomethylglycinate, use in the preparation of herbicides of the glyphosate type |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5117043A true US5117043A (en) | 1992-05-26 |
Family
ID=9369474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/388,570 Expired - Fee Related US5117043A (en) | 1988-08-18 | 1989-08-01 | Process for the preparation of n-sulfomethylglycinate |
Country Status (28)
| Country | Link |
|---|---|
| US (1) | US5117043A (fr) |
| EP (1) | EP0356353B1 (fr) |
| JP (1) | JPH02101059A (fr) |
| KR (1) | KR900003114A (fr) |
| CN (2) | CN1040362A (fr) |
| AT (1) | ATE82256T1 (fr) |
| AU (1) | AU622212B2 (fr) |
| BG (2) | BG60104B2 (fr) |
| BR (1) | BR8904242A (fr) |
| CS (1) | CS8904851A3 (fr) |
| DD (1) | DD283992A5 (fr) |
| DE (1) | DE68903455T2 (fr) |
| DK (1) | DK405389A (fr) |
| FI (1) | FI893866A (fr) |
| FR (1) | FR2635522B1 (fr) |
| GR (1) | GR3006300T3 (fr) |
| HK (1) | HK21693A (fr) |
| HU (1) | HUT51599A (fr) |
| IL (1) | IL91344A0 (fr) |
| MA (1) | MA21612A1 (fr) |
| NZ (1) | NZ230344A (fr) |
| OA (1) | OA09426A (fr) |
| PL (1) | PL284406A1 (fr) |
| PT (1) | PT91483B (fr) |
| RO (1) | RO103740B1 (fr) |
| TR (1) | TR24158A (fr) |
| YU (1) | YU161389A (fr) |
| ZA (1) | ZA896293B (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561091A (en) * | 1993-11-18 | 1996-10-01 | Mobil Oil Corporation | High activity polyethylene catalyst prepared from an alcohol and silicon tetrachloride |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3799758A (en) * | 1971-08-09 | 1974-03-26 | Monsanto Co | N-phosphonomethyl-glycine phytotoxicant compositions |
| US3835000A (en) * | 1972-12-21 | 1974-09-10 | Monsanto Co | Electrolytic process for producing n-phosphonomethyl glycine |
| US3868407A (en) * | 1973-11-21 | 1975-02-25 | Monsanto Co | Carboxyalkyl esters of n-phosphonomethyl glycine |
| US3950402A (en) * | 1972-05-31 | 1976-04-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| US4069048A (en) * | 1975-02-17 | 1978-01-17 | Fuji Photo Film Co., Ltd. | Diffusion transfer photographic materials with color developer scavenger |
| US4147719A (en) * | 1976-12-20 | 1979-04-03 | Monsanto Company | Process for producing N-phosphonomethylglycine salts |
| EP0019384A1 (fr) * | 1979-05-15 | 1980-11-26 | Imperial Chemical Industries Plc | Compositions pesticides |
-
1988
- 1988-08-18 FR FR8811141A patent/FR2635522B1/fr not_active Expired - Lifetime
-
1989
- 1989-08-01 US US07/388,570 patent/US5117043A/en not_active Expired - Fee Related
- 1989-08-07 CN CN89105602A patent/CN1040362A/zh active Pending
- 1989-08-10 DE DE8989420302T patent/DE68903455T2/de not_active Expired - Fee Related
- 1989-08-10 EP EP89420302A patent/EP0356353B1/fr not_active Expired - Lifetime
- 1989-08-10 AT AT89420302T patent/ATE82256T1/de not_active IP Right Cessation
- 1989-08-11 KR KR1019890011468A patent/KR900003114A/ko not_active Application Discontinuation
- 1989-08-14 TR TR89/0833A patent/TR24158A/xx unknown
- 1989-08-15 JP JP1210538A patent/JPH02101059A/ja active Pending
- 1989-08-15 MA MA21865A patent/MA21612A1/fr unknown
- 1989-08-16 FI FI893866A patent/FI893866A/fi not_active Application Discontinuation
- 1989-08-16 RO RO141304A patent/RO103740B1/ro unknown
- 1989-08-16 PL PL28440689A patent/PL284406A1/xx unknown
- 1989-08-17 BG BG095878A patent/BG60104B2/bg unknown
- 1989-08-17 BG BG089562A patent/BG50724A3/xx unknown
- 1989-08-17 AU AU40028/89A patent/AU622212B2/en not_active Ceased
- 1989-08-17 CS CS894851A patent/CS8904851A3/cs unknown
- 1989-08-17 YU YU01613/89A patent/YU161389A/xx unknown
- 1989-08-17 NZ NZ230344A patent/NZ230344A/en unknown
- 1989-08-17 IL IL91344A patent/IL91344A0/xx unknown
- 1989-08-17 DK DK405389A patent/DK405389A/da not_active Application Discontinuation
- 1989-08-17 ZA ZA896293A patent/ZA896293B/xx unknown
- 1989-08-18 OA OA59625A patent/OA09426A/fr unknown
- 1989-08-18 DD DD89331920A patent/DD283992A5/de not_active IP Right Cessation
- 1989-08-18 BR BR898904242A patent/BR8904242A/pt unknown
- 1989-08-18 PT PT91483A patent/PT91483B/pt not_active IP Right Cessation
- 1989-08-18 HU HU894243A patent/HUT51599A/hu unknown
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1992
- 1992-04-17 CN CN92102843A patent/CN1064868A/zh active Pending
- 1992-11-20 GR GR920400199T patent/GR3006300T3/el unknown
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1993
- 1993-03-11 HK HK216/93A patent/HK21693A/xx unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3799758A (en) * | 1971-08-09 | 1974-03-26 | Monsanto Co | N-phosphonomethyl-glycine phytotoxicant compositions |
| US3950402A (en) * | 1972-05-31 | 1976-04-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| US3835000A (en) * | 1972-12-21 | 1974-09-10 | Monsanto Co | Electrolytic process for producing n-phosphonomethyl glycine |
| US3868407A (en) * | 1973-11-21 | 1975-02-25 | Monsanto Co | Carboxyalkyl esters of n-phosphonomethyl glycine |
| US4069048A (en) * | 1975-02-17 | 1978-01-17 | Fuji Photo Film Co., Ltd. | Diffusion transfer photographic materials with color developer scavenger |
| US4147719A (en) * | 1976-12-20 | 1979-04-03 | Monsanto Company | Process for producing N-phosphonomethylglycine salts |
| EP0019384A1 (fr) * | 1979-05-15 | 1980-11-26 | Imperial Chemical Industries Plc | Compositions pesticides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5561091A (en) * | 1993-11-18 | 1996-10-01 | Mobil Oil Corporation | High activity polyethylene catalyst prepared from an alcohol and silicon tetrachloride |
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